Method for manufacture of amorphous silica-alumina composition in the presence of odso

ABSTRACT

A method for the preparation of an amorphous silica-alumina composition is provided that advantageously utilizes as a component oxidized disulfide oil, for example derived from a waste refinery stream of disulfide oil. The amorphous silica-alumina is formed from an aqueous mixture of an aluminum source, a silica source, oxidized disulfide oil, an alkali metal source and optionally a structure directing agent, which is heating under conditions and for a time effective to form the amorphous silica-alumina.

RELATED APPLICATIONS

Not applicable.

BACKGROUND OF THE INVENTION Field of the Invention

The present invention relates to a method of making an amorphoussilica-alumina composition.

Description of Related Art

Amorphous silica-alumina (ASA) is a catalytic material, or a support orco-support for a catalytic material, in many commercial applications.Numerous methods of manufacturing ASA are known, and it is appreciatedthat the physical and catalytic properties of ASA can be highlydependent upon the method by which it is manufactured.

Conventional processes for making ASA are known, for example asdisclosed in U.S. Pat. Nos. 4,500,645, 8,795,513 and 6,399,530, all ofwhich are incorporated by reference herein in their entireties.

Within a typical refinery, there are by-product streams that must betreated or otherwise disposed of. The mercaptan oxidation process,commonly referred to as the MEROX process, has long been employed forthe removal of the generally foul smelling mercaptans found in manyhydrocarbon streams and was introduced in the refining industry overfifty years ago. Because of regulatory requirements for the reduction ofthe sulfur content of fuels for environmental reasons, refineries havebeen, and continue to be faced with the disposal of large volumes ofsulfur-containing by-products. Disulfide oil (DSO) compounds areproduced as a by-product of the MEROX process in which the mercaptansare removed from any of a variety of petroleum streams includingliquefied petroleum gas, naphtha, and other hydrocarbon fractions. It iscommonly referred to as a ‘sweetening process’ because it removes thesour or foul smelling mercaptans present in crude petroleum. The term“DSO” is used for convenience in this description and in the claims, andwill be understood to include the mixture of disulfide oils produced asby-products of the mercaptan oxidation process. Examples of DSO includedimethyldisulfide, diethyldisulfide, and methylethyldisulfide.

The by-product DSO compounds produced by the MEROX unit can be processedand/or disposed of during the operation of various other refinery units.For example, DSO can be added to the fuel oil pool at the expense of aresulting higher sulfur content of the pool. DSO can be processed in ahydrotreating/hydrocracking unit at the expense of higher hydrogenconsumption. DSO also has an unpleasant foul or sour smell, which issomewhat less prevalent because of its relatively lower vapor pressureat ambient temperature; however, problems exist in the handling of thisoil.

Commonly owned U.S. Pat. No. 10,807,947 which is incorporated byreference herein in its entirety discloses a controlled catalyticoxidation of MEROX process by-products DSO. The resulting oxidizedmaterial is referred to as oxidized disulfide oil (ODSO). As disclosedin 10,807,947, the by-product DSO compounds from the mercaptan oxidationprocess can be oxidized, preferably in the presence of a catalyst. Theoxidation reaction products constitute an abundant source of ODSOcompounds, sulfoxides, sulfonates, sulfinates and sulfones. The oxidantcan be a liquid peroxide selected from the group consisting of alkylhydroperoxides, aryl hydroperoxides, dialkyl peroxides, diarylperoxides, peresters and hydrogen peroxide. The oxidant can also be agas, including air, oxygen, ozone and oxides of nitrogen. The catalystcan be a homogeneous water-soluble compound that is a transition metalcontaining an active species selected from the group consisting of Mo(VI), W (VI), V (V), Ti (IV), and combinations thereof.

The ODSO stream so-produced contains ODSO compounds as disclosed in U.S.Pat. No. 10,781,168 as a solvent (in general), in U.S. Pat. No.10,793,782 as an aromatics extraction solvent, and in U.S. Pat. No.10,927,318 as a lubricity additive, all of which are incorporated byreference herein in their entireties. In the event that a refiner hasproduced or has on hand an amount of DSO compounds that is in excess offoreseeable needs for these or other uses, the refiner may wish todispose of the DSO compounds in order to clear a storage vessel and/oreliminate the product from inventory for tax reasons.

Thus, there is a clear and long-standing need to provide an efficientand economical process for the treatment of the large volumes of DSOby-products and their derivatives to effect and modify their propertiesin order to facilitate and simplify their environmentally acceptabledisposal, and to utilize the modified products in an economically andenvironmentally friendly manner, and thereby enhance the value of thisclass of by-products to the refiner.

-   -   a. Despite the known ways to produce ASA materials, there        remains a need in the art for improved methods to produce ASA        materials, in particular using DSO by-products in an        economically and environmentally friendly manner.

SUMMARY

A method for the preparation of an amorphous silica-alumina compositionis provided that advantageously utilizes ODSO as a component, forexample derived from a waste refinery stream of disulfide oil. Theamorphous silica-alumina is formed from an aqueous mixture of analuminum source, a silica source, water soluble ODSO, an alkali metalsource and optionally a structure directing agent. The aqueous mixtureis heated under conditions and for a time effective to form theamorphous silica-alumina.

In certain embodiments of the present disclosure, the method forsynthesizing ASA comprises: forming an aqueous mixture of an aluminumsource, a silica source, water soluble ODSO, an alkali metal source andoptionally a structure directing agent; heating the mixture underconditions and for a time effective to form amorphous silica-alumina asa precipitate suspended in a supernatant as an intermediate suspension;and recovering the amorphous silica-alumina composition from theintermediate suspension.

In certain embodiments, the recovered amorphous silica-aluminacomposition is calcined. In certain embodiments, the intermediatesuspension has a pH of less than about 9, for example in the range ofabout 1-9. In certain embodiments, the alkali metal source is sodium andthe mass ratio of ODSO to sodium is greater than about 9, for example inthe range of about 9-75. In certain embodiments, the recovered amorphoussilica-alumina composition has a silica-to-alumina ratio in the range ofabout 20-1500.

The aluminum source comprises aluminates, alumina, other zeolites,aluminum colloids, boehmites, pseudo-boehmites, aluminum hydroxides,aluminum salts, aluminum alkoxides or alumina gels. The silica sourcecomprises sodium silicate (water glass), fumed silica, precipitatedsilica, colloidal silica, silica gels, zeolites, dealuminated zeolites,silicon hydroxides or silicon alkoxides. The optional structuredirecting agent can comprise quaternary ammonium cation compounds,bifunctional dicationic molecules containing a long aliphatic chain,dual-porogenic surfactants, silylated polyethylenimine polymers,amphiphilic organosilanes, or hydrophilic cationicpolyelectrolytes/polymers. In certain embodiments, the structuredirecting agent can comprise quaternary ammonium cation compoundsselected from the group consisting of tetramethylammonium (TMA) cationcompounds, tetraethylammonium (TEA) cation compounds,tetrapropylammonium (TPA) cation compounds, tetrabutylammonium (TBA)cation compounds, cetyltrimethylammonium (CTA) cation compounds, andcombinations thereof. In certain embodiments, the structure directingagent comprises bifunctional dicationic molecules selected from thegroup consisting of C₂₂₋₆₋₆, C₂₂₋₆₋₃, and poly(ethylene glycol).

In the above methods, the ODSO compounds can include 3 or more oxygenatoms; have 1 to 20 carbon atoms; have an average density greater thanabout 1.0 g/cc; and/or have an average boiling point greater than about80° C. In certain embodiments the ODSO compounds are selected from thegroup consisting of (R—SOO—SO—R′), (R—SOO—SOO—R′), (R—SO—SOO—OH),(R—SOO—SOO—OH), (R—SO—SO—OH), (R—SOO—SO—OH), and mixtures thereof, whereR and R′ can be the same or different and are alkyl groups comprising1-10 carbon atoms.

In the above methods, the homogeneous aqueous mixture can be formed byproviding the silica source; and, combining with the silica source, thealuminum oxide source, the alkali metal source and optionally thestructure directing agent, and the water soluble ODSO. The water solubleODSO can be added after the aluminum oxide source, the alkali metalsource, and optionally the structure directing agent, or the watersoluble ODSO can first be combined with the aluminum oxide source, thealkali metal source and optionally the structure directing agent, andthen the resulting mixture combined with the silica source.

In the above methods, the homogeneous aqueous mixture can be formed byproviding the aluminum oxide source, the alkali metal source andoptionally the structure directing agent as a first aqueous mixture; andcombining the first mixture with the silica source and the water solubleODSO. The water soluble ODSO can be added after the silica source; orthe water soluble ODSO can first be combined with the silica source, andthen the resulting mixture combined with the first mixture.

In the above methods, the homogeneous aqueous mixture can be formed bycombining the water soluble ODSO with the silica source to form a firstmixture; and combining with the first mixture the aluminum oxide source,the alkali metal source and optionally the structure directing agent.

In the above methods, the homogeneous aqueous mixture can be formed bycombining the water soluble ODSO with the aluminum oxide source, thealkali metal source and optionally the structure directing agent to forma first mixture; and combining with the first mixture the silica source.

In the above methods, an effective quantity of water for the homogeneousaqueous mixture is provided by using a water-containing silica source,and/or by using an aqueous mixture of the aluminum oxide source, thealkali metal source and optionally the structure directing agent.

Still other aspects, embodiments, and advantages of these exemplaryaspects and embodiments, are discussed in detail below. Moreover, it isto be understood that both the foregoing information and the followingdetailed description are merely illustrative examples of various aspectsand embodiments, and are intended to provide an overview or frameworkfor understanding the nature and character of the claimed aspects andembodiments. The accompanying drawings are included to provideillustration and a further understanding of the various aspects andembodiments, and are incorporated in and constitute a part of thisspecification. The drawings, together with the remainder of thespecification, serve to explain principles and operations of thedescribed and claimed aspects and embodiments.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention will be described in further detail below and withreference to the attached drawings in which the same or similar elementsare referred to by the same number, and where:

FIG. 1 shows X-ray diffraction patterns of calcined amorphoussilica-alumina materials synthesized using ODSO, wherein diffractogramsare provided for different ratios of ODSO/Na;

FIG. 2 is a plot of thermogravimetric (TGA) and derivativethermogravimetric (DTG) mass loss profiles of the as-made amorphoussilica-alumina products from Examples 1-2 using ODSO and water, and theas-made crystalline zeolite of comparative Example 1 using water only;

FIG. 3 is a plot of normalized yield as a function of ODSO/Na ratios,indicating crystalline or amorphous material;

FIG. 4 is a plot of ODSO/Na ratios against ODSO mass demonstratingtransition between crystalline products and amorphous products; and

FIG. 5 shows scanning electron microscopy images of the calcinedamorphous silica-alumina materials synthesized in the presence of ODSOand water.

DETAILED DESCRIPTION

Methods for the preparation of an ASA composition are provided.Effective quantities of water soluble ODSO, an aluminum source, a silicasource, an alkali metal source, and an optional structure directingagent are formed as a homogeneous aqueous mixture. The components aremixed for an effective time and under conditions suitable to form thehomogeneous aqueous mixture. The chronological sequence of mixing canvary, with the objective being a highly homogenous distribution of thecomponents in an aqueous mixture. The homogeneous aqueous mixture isheated under conditions and for a time effective to form amorphoussilica-alumina as a precipitate suspended in a supernatant. Theamorphous silica-alumina composition is recovered from the intermediatesuspension of the precipitate in the supernatant, for example byfiltration, washing and drying. In certain embodiments, the recoveredprecipitate is calcined at a suitable temperature, temperature ramp rateand for a suitable period of time at to realize ASA.

In certain embodiments, the homogeneous aqueous mixture is formed by:providing the silica source; combining the aluminum oxide source, thealkali metal source and optionally the structure directing agent; andcombining the water soluble ODSO. Alternatively, the water soluble ODSOis combined with the aluminum oxide source, the alkali metal source andoptionally the structure directing agent, and that mixture is combinedwith the silica source.

In certain embodiments, the homogeneous aqueous mixture is formed by:providing the aluminum oxide source, the alkali metal source andoptionally the structure directing agent as a mixture; combining thesilica source; and combining the water soluble ODSO. Alternatively, thewater soluble ODSO is combined with the silica source, and that mixtureis combined with the aluminum oxide source, the alkali metal source andoptionally the structure directing agent.

In certain embodiments, the homogeneous aqueous mixture is formed by:combining the water soluble ODSO with the silica source to form amixture; and that mixture is combined with the aluminum oxide source,the alkali metal source and optionally the structure directing agent.

In certain embodiments, the homogeneous aqueous mixture is formed by:combining the water soluble ODSO with the aluminum oxide source, thealkali metal source and optionally the structure directing agent to forma mixture; and that mixture is combined with the silica source.

The homogeneous aqueous mixture of the aluminum source, silica source,ODSO and optional structure directing agent, formed from any of theabove chronological sequences of component addition, is heated underconditions and for a time effective to form amorphous silica-alumina asa precipitate suspended in a supernatant. The amorphous silica-aluminacomposition is recovered from the intermediate suspension of theprecipitate in the supernatant, for example by filtration, washing anddrying. In certain embodiments, the recovered precipitate is calcined ata suitable temperature, temperature ramp rate and for a suitable periodof time at to realize ASA.

An effective quantity of water for the aqueous environment compound canbe provided by using a water-containing silica source such as colloidalsilica, and/or by using an aqueous mixture of the aluminum oxide source,the alkali metal source and optionally the structure directing agent.These components are added with water to the reaction vessel prior toheating. Typically, water allows for adequate mixing to realize a morehomogeneous distribution of the sol-gel components, which ultimatelyproduces a more desirable product with uniform structural phases ormorphologies. Insufficient mixing could result in undesirable “pockets”of highly concentrated sol-gel components and this may lead toimpurities in the form of different structural phases or morphologies.Water also determines the yield per volume.

Certain ratios of materials are provided to attain the effectivequantities of components. An effective SAR in the synthesized ASAincludes but is not limited to ratios in the range of about 20-1500,20-1000, 20-500, 25-1500, 25-1000, 25-500, 50-1500, 50-1000, 50-500,100-1500, 100-1000 or 100-500. In certain embodiments, an effectiveamount of structure directing agent is used, for example at a molarratio (normalized to 1 mole of Al₂O₃) in the range of about 0-75, 0-50,0-30, 0.1-75, 0.1-50, 0.1-30, 2.5-75, 2.5-50, 2.5-30, 5-75, 5-50 or5-30. In addition, an effective amount of alkali metal is used so as tomaintain a pH level of less than or equal to about 9, for example in therange of about 1-9, 2-9, 1-8 or 2-8 in the sol-gel solution (theamorphous silica-alumina as a precipitate suspended in a supernatant asan intermediate suspension). It is noted that in the process herein, thepH is reduced by the presence of ODSO, therefore, the quantity of thealkali metal source, such as sodium in the form of NaOH, can be adjustedaccordingly to give the desired added to provide the desired pH. Aneffective mass ratio of ODSO/Na is greater than or equal to about 9, forexample in the range of about 9-75.

The aluminum source can comprise, without limitation, one or more ofaluminates, alumina, other zeolites, aluminum colloids, boehmites,pseudo-boehmites, aluminum salts such as aluminum sulfate and aluminachloride, aluminum hydroxides and alkoxides, alumina gels. For example,suitable materials as aluminum sources are commercially available fromSasol, for instance high purity aluminas (CERALOX) and alumina hydrates(PURAL and CAPITAL), boehmites (DISPERSAL and DISPAL), andsilica-alumina hydrates (SIRAL) and the corresponding oxides (SIRALOX).

The silica source can comprise, without limitation, one or more ofsilicates including sodium silicate (water glass), fumed silica(typically pure silica in powder form), precipitated silica, colloidalsilica (silica particles suspended in water), silica gels, zeolites,dealuminated zeolites, and silicon hydroxides and alkoxides. Silicasources resulting in a high relative yield are preferred. For instance,suitable materials as silica sources are commercially from Cabot (forexample, fumed silica) and Ludox (for example, colloidal silica).

The disclosed processes for synthesizing ASA can occur in the absence orpresence of a structure directing agent. Effective structure directingagents include one or more of quaternary ammonium cation compounds(including one or more of tetramethylammonium (TMA) cation compounds,tetraethylammonium (TEA) cation compounds, tetrapropylammonium (TPA)cation compounds, tetrabutylammonium (TBA) cation compounds,cetyltrimethylammonium (CTA) cation compounds. The cation can be pairedwith one or more of a hydroxide anion (for example, TPAOH or CTAOH), abromide anion (for example, TPAB or CTAB), or an iodide anion. Incertain embodiments the structure directing agents include bifunctionaldicationic molecules containing a long aliphatic chain (for exampleC₂₂H₄₅—N⁺(CH₃)₂—C₆H₁₂—N⁺(CH₃)₂—C₆H₁₃, denoted C₂₂₋₆₋₆,C₂₂H₄₅—N⁺(CH₃)₂—C₆H₁₂—N⁺(CH₃)₂—C₃H₇, denoted C₂₂₋₆₋₃, or a poly(ethyleneglycol)), dual-porogenic surfactants, silylated polyethyleniminepolymers, amphiphilic organosilanes, or hydrophilic cationicpolyelectrolytes/polymers such as poly(diallyldimethylammonium chloride)(PDADMAC).

The disclosed processes for synthesizing ASA occur in the presence of amineralizer as the alkali metal source selected from the groupconsisting of NaOH, KOH, RbOH, LiOH, CsOH and combinations thereof. Incertain embodiments a Na-based mineralizer is selected. Note that thealkali metal source is provide as a hydroxide, but in embodiments hereinwhere the ratio is expressed based on the mass of the alkali, it is themetal itself. For instance, when the alkali is NaOH, the ODSO/Na ratiois determined by dividing the mass of the ODSO by the mass of the Naportion of NaOH, that is, about 57.5% of the NaOH mass.

In the process herein, one or more ODSO compounds are used in thesynthesis of ASA. The one or more ODSO compounds can include compoundsof the general formulae R—SOO—SO—R′, R—SOO—SOO—R′, R—SO—SOO—OH,R—SOO—SOO—OH, R—SO—SO—OH, R—SOO—SO—OH, and mixtures thereof, where R andR′ can be the same or different and are alkyl groups comprising 1-10carbon atoms. In certain embodiments, the R and R′ are methyl and/orethyl groups. The one or more ODSO compounds used in the synthesis ofASA generally include ODSO compounds having 3 or more oxygen atoms. Incertain embodiments, one or more ODSO compounds used in the synthesis ofASA include ODSO compounds having 1 to 20 carbon atoms. In certainembodiments, one or more ODSO compounds used in the synthesis of ASAinclude ODSO compounds having an average density greater than about 1.0g/cc. In certain embodiments, one or more ODSO compounds used in thesynthesis of ASA include ODSO compounds having an average boiling pointgreater than about 80° C.

In certain embodiments ODSO compounds used in the synthesis of ASAcomprise all or a portion of water-soluble ODSO compounds contained inan oxidation effluent stream that is obtained by oxidation of DSOcompounds from a MEROX process, as disclosed in U.S. Pat. Nos.10,807,947 and 10,781,168 and as incorporated herein by reference above.Table 1 identifies certain water-soluble ODSO compounds that are formedby oxidation of DSO obtained from MEROX by-products.

TABLE 1 ODSO Name Formula Structure Examples Dialkyl-sulfonesulfoxide Or1,2-alkyl-alkyl-disulfane 1,1,2-trioxide (R—SOO—SO—R′)

1,2-Dimethyldisulfane 1,1,2- trioxide Dialkyl-disulfone Or 1,2alkyl-alkyl-disulfane 1,1,2,2-tetraoxide (R—SOO—SOO—R′)

1,2-Dimethyldisulfane 1,1,2,2- tetraoxide Alkyl-sulfoxidesulfonate(R—SO—SOO—OH)

Methylsulfanesulfonic acid oxide Alkyl-sulfonesulfonate (R—SOO—SOO—OH)

1-Hydroxy-2-methyldisulfane 1,1,2,2-tetraoxide Alkyl-sulfoxidesulfinate(R—SO—SO—OH)

l-Hydroxy-2-methyldisulfane 1,2-dioxide Alkyl-sulfonesulfinate(R—SOO—SO—OH)

Methylsulfanesulfinic acid dioxide R and R′ can be the same or differentalkyl groups comprising 1-10 carbon atoms.

In certain embodiments, the ODSO compounds are contained in a mixturefrom oxidation of DSO compounds, comprising alkyl-sulfoxidesulfonate(R—SO—SOO—OH), alkyl-sulfonesulfonate (R—SOO—SOO—OH),alkyl-sulfoxidesulfinate (R—SO—SO—OH) and alkyl-sulfonesulfinate(R—SOO—SO—OH), for example, similar to those obtained as “Composition 2”in U.S. Pat. No. 10,781,168 as incorporated herein by reference above.

The below examples and data are exemplary. It is to be understood thatother aluminum sources, silica sources, bases and structure directingagents can be used as compared to the example.

In the synthesis steps for producing ASA herein, the sequence of addingthe components is described above, but can be varied. In certainembodiments, the aluminum source, the alkali metal source and optionallythe structure directing agent are formed into an aqueous solution, towhich the ODSO is added, and then the silica, since addition of thesilica source forms a thick gel. In other embodiments, the ODSO can beadded to the silica source, and that mixture is added to an aqueoussolution of the aluminum source, the alkali metal source and thestructure directing agent. In other embodiments, the aluminum source,alkali metal source and optionally the structure directing agent areformed into an aqueous solution, to which the ODSO is added and thismixture added to the silica source. In other embodiments, the ODSO canbe added to the silica source to which that mixture receives an aqueoussolution of the aluminum source, alkali metal source and optionally thestructure directing agent.

The temperature and pressure conditions, and residence time, for themixing steps described herein to produce the intermediate suspension ofprecipitate in the supernatant that is used for producing ASA aresimilar to those used in typical ZSM-5 synthesis, for example, where thesol-gel is prepared at ambient temperature and pressure (for instanceabout 20° C. and about 1 standard atmosphere). The mixing time issufficient to realize a homogeneous distribution of the sol-gelcomponents. In certain embodiments the sol-gel can be aged before beingsubjected to subsequent hydrothermal treatment, for example for a periodof about 0-24, 0-5, 0.5-24 or 0.5-5 hours. Hydrothermal treatment isthen carried out at a temperature in the range of about 100-180° C. andat atmospheric or autogenous pressure, and for a time period within therange of about 3 hours to 5 days.

The products are washed, for example with water at a suitable quantity,for example at about twice the volume of the sol-gel solution. The washcan be at a temperature of from about 20-80° C. at atmospheric pressureor under vacuum. The wash can continue until the pH of the filtrateapproaches 7. The solids are recovered by filtration, for instance,using known techniques such as centrifugation, gravity, vacuumfiltration, filter press, or rotary drums, and dried, for example at atemperature of up to about 110 or 150° C.

The conditions for calcination to produce ASA herein can includetemperatures in the range of about 450-700, 450-600, 500-700 or 500-600°C., atmospheric pressure, and a time period of about 3-24, 3-18, 6-24 or6-18 hours. Calcining can occur with ramp rates in the range of fromabout 0.1-10, 0.1-5, 0.1-3, 1-10, 1-5 or 1-3° C. per minute. In certainembodiments calcination can have a first step ramping to a temperatureof between about 100-150° C. with a holding time of from about 2-24hours (at ramp rates of from about 0.1-5, 0.1-3, 1-5 or 1-3° C. per min)before increasing to a higher temperature with a final holding time inthe range of about 2-24 hours.

EXAMPLES Comparative Example 1

Aluminum nitrate nonahydrate (0.2633 g) was weighed into a Teflon liner(45 ml). Thereafter, 0.7750 g of a 50 wt. % sodium hydroxide solutionand 7.0469 g tetrapropylammonium hydroxide (TPAOH) were added and themixture stirred. Next, distilled water (3.3005 g) was added and themixture was maintained under stirring. Finally, the silica source,5.2430 g of Ludox AS-50, SiO₂ content of 40 wt. %, was added and themixture stirred until homogeneous.

The Teflon liner was positioned within an autoclave and transferred toan oven and heated to a temperature of 175° C. whilst rotating theautoclave. The autoclave was maintained at isothermal conditions for 18hours.

The product was filtered and washed with distilled water before dryingat 110° C. The dry mass was 1.3906 g. The inorganic content determinedby thermogravimetric (TGA) analysis was 87.78%. Hence, a product(zeolite) yield of 1.2207 g was obtained.

The as-made sample from Comparative Example 1 was calcined at 550° C.(1° C./min ramp rate) for 8 hours to realize a porous ZSM-5 zeolite.

Example 1

Aluminum nitrate nonahydrate (0.2620 g) was weighed into a Teflon liner(45 ml). Thereafter, 0.7782 g of a 50 wt. % sodium hydroxide solutionand 7.0381 g tetrapropylammonium hydroxide (TPAOH) were added and themixture stirred. Next, ODSO (3.2703 g) was added and the mixture wasmaintained under stirring. The ODSO used in this example are thoseobtained as “Composition 2” in U.S. Pat. No. 10,781,168, incorporatedherein by reference above. Finally, the silica source, 5.2634 g of LudoxAS-50, SiO₂ content of 40 wt. %, was added and the mixture stirred untilhomogeneous.

The Teflon liner was positioned within an autoclave and transferred toan oven and heated to a temperature of 175° C. whilst rotating theautoclave. The autoclave was maintained at isothermal conditions for 18hours.

Thereafter, the product was filtered and washed with distilled waterbefore drying at 110° C. The dry mass was 1.9532 g. The inorganiccontent determined by thermogravimetric (TGA) analysis was 91.65%.Hence, a product yield of 1.7901 g was obtained.

Example 2

Aluminum nitrate nonahydrate (0.2605 g) was weighed into a Teflon liner(45 ml). Thereafter, 0.7468 g of a 50 wt. % sodium hydroxide solutionand 7.0192 g tetrapropylammonium hydroxide (TPAOH) were added and themixture stirred. Next, distilled water (1.3271 g) and ODSO (1.9722 g)were added and the mixture was maintained under stirring. The ODSO usedin this example are those obtained as “Composition 2” in U.S. Pat. No.10,781,168, incorporated herein by reference above. Finally, the silicasource, 5.2148 g of Ludox AS-50, SiO₂ content of 40 wt. %, was added andthe mixture stirred until homogeneous.

The Teflon liner was positioned within an autoclave and transferred toan oven and heated to a temperature of 175° C. whilst rotating theautoclave. The autoclave was maintained at isothermal conditions for 18hours.

Thereafter, the product was filtered and washed with distilled waterbefore drying at 110° C. The dry mass was 2.1920 g. The inorganiccontent determined by thermogravimetric (TGA) analysis was 94.19%.Hence, a product yield of 2.0646 g was obtained.

The as-made samples from Examples 1 and 2 were calcined at 550° C. (1°C./min ramp rate) for 8 hours to realize porous ASA materials.

FIG. 1 shows the x-ray diffraction patterns of the calcined amorphousASA materials from Examples 1 and 2. Both diffractograms show theamorphous nature of the materials since there are no sharp peaks andonly a broad peak at approximately 25°/2θ, representative of amorphoussilica.

Additionally, the product yield is increased for the ASA materials whencompared with the product (zeolite) synthesized only in the presence ofwater in the absence of ODSO. The highest yield obtained is approximateto the transition region between crystalline and amorphous. Furtherincreasing the ODSO/Na mass ratio reduces the product yield. Productyield is calculated based on the dry-mass of the as-made materialsmultiplied by the % of inorganic content determined fromthermogravimetric analysis (FIG. 2 , FIG. 3 and Table 2). FIG. 4 showsthe transition between crystalline products and amorphous products as afunction of the ODSO/Na mass ratio. The morphology of the ASA materialsis non-defined likely as a result of the amorphous nature, as shown inFIG. 5 , which are scanning electron microscopy images of the calcinedamorphous silica-alumina materials using ODSO.

The relative yields are 35% to 80% greater than the equivalent yieldproduced for the corresponding crystalline zeolite formed in the absenceof any ODSO, that is, a water-only synthesis (see FIG. 3 ).

TABLE 2 Normalized zeolite yield as a function of the ODSO/Na ratio.ODSO/Na Ratio (w/w) Normalized Yield Phase 0 1.00 Zeolite 9.19 1.69Amorphous silica- alumina 14.62 1.47 Amorphous silica- aluminaNormalized yield is based on the dry mass of the as-made materialsmultiplied by the inorganic content determined from thermogravimetricanalysis. An ODSO/Na ratio = 0 is a water-only synthesis in the absenceof ODSO.

The methods and compositions of the present invention have beendescribed above and in the attached drawings; however, modificationswill be apparent to those of ordinary skill in the art and the scope ofprotection for the invention is to be defined by the claims that follow.

1. A method for the preparation of an amorphous silica-aluminacomposition comprising: forming a homogeneous aqueous mixture of watersoluble oxidized disulfide oil (ODSO), a silica source, an aluminumsource, an alkali metal source and optionally a structure directingagent; heating the homogeneous aqueous mixture under conditions and fora time effective to form amorphous silica-alumina as a precipitatesuspended in a supernatant as an intermediate suspension; and recoveringthe amorphous silica-alumina composition from the intermediatesuspension.
 2. The method of claim 1, further comprising calcining therecovered amorphous silica-alumina composition.
 3. The method of claim1, wherein the intermediate suspension has a pH of less than about
 9. 4.The method of claim 1, wherein the alkali metal source is sodium and themass ratio of ODSO to sodium is greater than about
 9. 5. The method ofclaim 1, wherein the recovered amorphous silica-alumina composition hasa silica-to-alumina ratio in the range of about 20-1500.
 6. The methodas in claim 1, wherein the aluminum source comprises aluminates,alumina, other zeolites, aluminum colloids, boehmites, pseudo-boehmites,aluminum hydroxides, aluminum salts, aluminum alkoxides or alumina gels.7. The method as in claim 1, wherein the silica source comprises sodiumsilicate (water glass), fumed silica, precipitated silica, colloidalsilica, silica gels, zeolites, dealuminated zeolites, silicon hydroxidesor silicon alkoxides.
 8. The method as in claim 1, wherein a structuredirecting agent is used, and wherein the structure directing agentcomprises quaternary ammonium cation compounds, bifunctional dicationicmolecules containing a long aliphatic chain, dual-porogenic surfactants,silylated polyethylenimine polymers, amphiphilic organosilanes, orhydrophilic cationic polyelectrolytes/polymers.
 9. The method as inclaim 8, wherein the structure directing agent comprises quaternaryammonium cation compounds selected from the group consisting oftetramethylammonium (TMA) cation compounds, tetraethylammonium (TEA)cation compounds, tetrapropylammonium (TPA) cation compounds,tetrabutylammonium (TBA) cation compounds, cetyltrimethylammonium (CTA)cation compounds and combinations thereof.
 10. The method as in claim 8,wherein the structure directing agent comprises bifunctional dicationicmolecules selected from the group consisting of C₂₂₋₆₋₆, C₂₂₋₆₋₃, andpoly(ethylene glycol).
 11. The method of claim 1, wherein the ODSOcomprises ODSO compounds having 3 or more oxygen atoms.
 12. The methodof claim 1, wherein the ODSO comprises ODSO compounds having 1 to 20carbon atoms.
 13. The method of claim 1, wherein the ODSO has an averagedensity greater than about 1.0 g/cc.
 14. The method of claim 1, whereinthe ODSO has an average boiling point greater than about 80° C.
 15. Themethod of claim 1, wherein the ODSO comprises ODSO compounds selectedfrom the group consisting of (R—SOO—SO—R′), (R—SOO—SOO—R′),(R—SO—SOO—OH), (R—SOO—SOO—OH), (R—SO—SO—OH), (R—SOO—SO—OH), and mixturesthereof, where R and R′ can be the same or different and are alkylgroups comprising 1-10 carbon atoms.
 16. The method of claim 1, whereinthe homogeneous aqueous mixture is formed by: providing the silicasource; and combining with the silica source the aluminum oxide source,the alkali metal source, and optionally the structure directing agent;and the water soluble ODSO; wherein the water soluble ODSO is addedafter the aluminum oxide source, the alkali metal source, and optionallythe structure directing agent; or wherein the water soluble ODSO isfirst combined with the aluminum oxide source, the alkali metal sourceand optionally the structure directing agent, and then combined with thesilica source; and wherein an effective quantity of water for thehomogeneous aqueous mixture is provided by using a water-containingsilica source, and/or by using an aqueous mixture of the aluminum oxidesource, the alkali metal source and optionally the structure directingagent.
 17. The method of claim 1, wherein the homogeneous aqueousmixture is formed by: providing the aluminum oxide source, the alkalimetal source and optionally the structure directing agent as a firstmixture; and combining the first mixture with the silica source and thewater soluble ODSO; wherein the water soluble ODSO is added after thesilica source; or wherein the water soluble ODSO is first combined withthe silica source, and then combined with the first mixture, wherein aneffective quantity of water for the homogeneous aqueous mixture isprovided by using a water-containing silica source, and/or by using anaqueous mixture of the aluminum oxide source, the alkali metal sourceand optionally the structure directing agent.
 18. The method of claim 1,wherein the homogeneous aqueous mixture is formed by: combining thewater soluble ODSO with the silica source to form a first mixture; andcombining the first mixture with the aluminum oxide source, alkali metalsource and optionally the structure directing agent; wherein aneffective quantity of water for the homogeneous aqueous mixture isprovided by using a water-containing silica source, and/or by using anaqueous mixture of the aluminum oxide source, the alkali metal sourceand optionally the structure directing agent.
 19. The method of claim 1,wherein the homogeneous aqueous mixture is formed by: combining thewater soluble ODSO with the aluminum oxide source, the alkali metalsource and optionally the structure directing agent to form a firstmixture; and combining the first mixture with the silica source; whereinan effective quantity of water for the homogeneous aqueous mixture isprovided by using a water-containing silica source, and/or by using anaqueous mixture of the aluminum oxide source, the alkali metal sourceand optionally the structure directing agent.
 20. The method of claim 1,wherein an effective quantity of water for the homogeneous aqueousmixture is provided by using a water-containing silica source, and/or byusing an aqueous mixture of the aluminum oxide source, the alkali metalsource and optionally the structure directing agent.